Precursors for silicon dioxide gap fill

ABSTRACT

A full fill trench structure comprising a microelectronic device substrate having a high aspect ratio trench therein and a full filled mass of silicon dioxide in the trench, wherein the silicon dioxide is of a substantially void-free character and has a substantially uniform density throughout its bulk mass. A corresponding method of manufacturing a semiconductor product is described, involving use of specific silicon precursor compositions for use in full filling a trench of a microelectronic device substrate, in which the silicon dioxide precursor composition is processed to conduct hydrolysis and condensation reactions for forming the substantially void-free and substantially uniform density silicon dioxide material in the trench. The fill process may be carried out with a precursor fill composition including silicon and germanium, to produce a microelectronic device structure including a GeO 2 /SiO 2  trench fill material. A suppressor component, e.g., methanol, may be employed in the precursor fill composition, to eliminate or minimize seam formation in the cured trench fill material.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present invention claims the benefit of priority under 35 USC 119 ofU.S. Provisional Patent Application No. 60/946,968 filed Jun. 28, 2007and U.S. Provisional Patent Application No. 61/055,809 filed May 23,2008. The disclosures of said U.S. Provisional Patent Applications arehereby incorporated herein by reference, in their entireties, for allpurposes.

FIELD OF THE INVENTION

The present invention relates to trench structures of microelectronicdevices and methods for fabricating same, and to precursors havingutility for forming silicon dioxide full-fill high aspect ratio trenchstructures in which the silicon dioxide precursor is flow filled in thetrench and cures rapidly at low temperature to form silicon dioxide of asubstantially void-free condition with substantially uniform densitythroughout its bulk volume.

DESCRIPTION OF THE RELATED ART

As dimensions in integrated circuits continue to decrease,correspondingly narrower trenches with increasing aspect ratios arerequired. Current processes to deposit silicon dioxide in trenchesemploy chemical vapor deposition. However, with technology nodesdecreasing to below 65 nm, it becomes progressively more difficult todeposit silicon dioxide in narrow trenches without introducing voids inthe deposited material.

Faced with such difficulty, a low-temperature flow-fill method in acontrolled humidity environment or with an oxidant co-reactant isdesired for curing, since elevated temperature hydrolysis andcondensation reactions are prone to form voids and cracks in the productsilicon dioxide material. Voids, cracks, and other defects in turncreate inhomogenieties in the dielectric material that adversely affectdevice performance. A condensed matrix material that exhibits lowshrinkage during thermal curing therefore is necessary in order toprevent cracking.

Uniform material densification in the narrow trenches is also a problemwith conventionally available silicon dioxide precursors due todiffusion-limited oxidation that occurs during their curing.

Normally a high temperature (600-1200° C.) thermal anneal stage is usedto form SiO₂. A low temperature process is preferred, due to hightemperature incompatibilities with other structures, materials, andprocesses in the integrated circuit or memory device that lead to adegraded device with poor performance when high temperature annealing isemployed. Further, high temperature annealing increases the overallthermal budget of the process, and is disadvantageous for such reason.

Conventional precursors used in the art to form oxide layers insemiconductors, which are characterized by the aforementioned problems,include: silane or methylsilane, as cured with hydrogen peroxide;polysilazane, as cured with ozone or oxic plasma;tetraethylorthosilicate, as cured with water; and hexachlorodisilane(HCDS), as cured with pyridine and water.

Although certain alkoxysilanes, such as triethoxysilane, have beenutilized as silicon dioxide precursors, such precursors hydrolyze slowlyin moist air and the condensation rate of silica at neutral pH isrelatively slow. Precursors with hydrolyzable or labile groups caninduce crosslinking, thereby generating a dense SiO₂ matrix withimproved density, increased mechanical strength, and enhanced CMP(chemical mechanical polishing) and HF etch resistances. Even thoughwater vapor annealing is effective for densifying the oxide film, insome integrations in which the transistor is formed before the isolationmaterial is deposited, water annealing has the significant drawback thatit causes oxidation around the transistor that degrades performance.

One possible composition for fill of memory device trenches istetraethylorthosilicate (TEOS) as cured thermally with ozone, whichholds the potential for achieving extremely conformal films. SuchTEOS/ozone process, however, has the substantial deficiency that whilethe resultant composition can be made to fully fill the trench, itinherently leaves a seam where the growths from the trench sidewallsmeet one another. This seam is a common weak region with enhancedremoval rates when exposed to cleaning chemistries in subsequent deviceprocessing.

A precursor that can be flow-filled and hydrolyzed rapidly at lowtemperatures, then quickly condensed to form dense SiO₂ in the trenchbefore the formation of a skin layer, would achieve a substantialadvance in the art.

Another issue related to such trench filling is that although watervapor annealing

SUMMARY OF THE INVENTION

The present invention relates to microelectronic device trenchstructures and fabrication methods therefor, and silicon dioxideprecursors suitable for forming silicon dioxide full-fill high aspectratio trench structures in which the precursor is flow filled in thetrench and cures rapidly at low temperature to form silicon dioxide of asubstantially void-free condition with substantially uniform densitythroughout its bulk volume.

In one aspect, the invention relates to a full fill trench structurecomprising a microelectronic device substrate having a high aspect ratiotrench therein and a full filled mass of silicon dioxide in said trench,said silicon dioxide being of a substantially void-free character andhaving a substantially uniform density throughout its bulk mass.

In another aspect, the invention relates to a method of manufacturing asemiconductor product, including providing a microelectronic devicesubstrate having a trench therein, and full filling the trench with asilicon dioxide precursor composition, and processing the silicondioxide precursor composition to form a full fill mass of silicondioxide in the trench, wherein the silicon dioxide precursor compositioncomprises a precursor silicon compound selected from the groupconsisting of:

(i) aminosilanes of the formula (R¹R²N)_(4-x)SiR_(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R, R¹, and R²is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(ii) alkoxysilanes of the formula (RO)_(4-x)SiR¹ _(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iii) alkoxydisilanes of the formula (RO)_(3-x)R¹ _(x)Si—Si(OR)_(3-x)R¹_(x) wherein x is an integer having a value in a range of from 0 to 2,and each R and R¹ is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iv) aminodisilanes of the formula(R¹R²N)_(3-x)R_(x)Si—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched or unbranched C₁-C₆alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(v) aminodisiloxanes of the formula(R¹R²N)_(3-x)R_(x)Si—O—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(vi) alkoxydisiloxanes of the formula (RO)_(3-x)(R¹_(x)Si—O—Si(OR)_(3-x)R¹ _(x), wherein x is an integer having a value ina range of from 0 to 2, and each R and R¹ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(vii) aminodisilazanes of the formula(R¹R²N)_(3-x)R_(x)Si—NH—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(viii) alkoxydisilazanes of the formula(RO)_(3-x)Si—NH—Si(OR)_(3-x)R_(x), wherein x is an integer having avalue in a range of from 0 to 2, and each R and R¹ is independentlyselected from among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(ix) chloroaminosilanes of the formulae Cl_(4-x)Si(NR¹R²)_(x), wherein xis an integer having a value in a range of from 0 to 3,(R¹R²N)_(3-x)Cl_(x)Si—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of 1 or 2, (R¹R²N)_(3-x)Cl_(x)Si—O—Si(NR¹R²)_(3-x)Cl_(x),wherein x is an integer having a value of 1 or 2, and(R¹R²N)_(3-x)Cl_(x)Si—NH—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of from 1 or 2, and each R¹ and R² is independentlyselected from among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(x) cyclosiloxanes and cyclosilazanes of the formulae:

wherein n is an integer having a value in the range of from 0 to 4, andeach R¹ and R² is selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ dialkylamino, andC₁-C₆ alkoxide;(xi) linear polysiloxanes and polysilazanes;(xii) silicon compounds of general formulae R_(4-x)SiL_(x) wherein x isan integer having a value of from 1 to 3, andL_(3-x)R_(x)Si—SiL_(3-x)R_(x), wherein x is an integer having a value offrom 0 to 2, L is selected from isocyanato (NCO), methylethylketoxime(R¹R²C═N—O—), trifluoroacetate (CF₃OCO), triflate (CF₃SO₃), acyloxy(ROCO), β-diketonate (R¹COCHCOR²), β-diketiminate(R¹CNR²CHCOR³),β-diiminate (R¹CNR²CHCNR²R³), amidinate (RC(NR¹)₂), guanidinate{(R¹R²N)C(NR³)₂}, alkylamino (NR¹R²), hydride, alkoxide (RO), andformato (HCOO) and each R, R¹, R², and R³ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(xiii) oxiranylsilanes of the formulae

wherein x is an integer having a value in a range of from 0 to 3, n isan integer having a value in a range of 0 to 3, and each R¹, R², and R³is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ alkylamino, and C₁-C₆alkoxide;(xiv) silicon precursors containing ethylacetate groups, of the formula(ROCOCH₂CH₂)_(x)Si(OR¹)_(4-x), wherein x is an integer having a value ina range of from 1 to 4, and each of R and R¹ is independently selectedfrom among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(xv) (tBuHN)₂(H₂N)Si—Si(NH₂)(NHtBu)₂ wherein tBu is tertiary butyl; and(xvi) pre-polymer partial hydrolysis products of the foregoing compounds(i)-(xv).

In a still further aspect, the invention relates to a method ofdepositing silicon dioxide on a substrate, comprising contacting asubstrate with a vapor of a precursor silicon compound selected from thegroup consisting of:

(i) aminosilanes of the formula (R¹R²N)_(4-x)SiR_(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R, R¹, and R²is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(ii) alkoxysilanes of the formula (RO)_(4-x)SiR¹ _(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iii) alkoxydisilanes of the formula (RO)_(3-x)R¹ _(x)Si—Si(OR)_(3-x)R¹_(x), wherein x is an integer having a value in a range of from 0 to 2,and each R and R¹ is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iv) aminodisilanes of the formula(R¹R²N)_(3-x)R_(x)Si—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched or unbranched C₁-C₆alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(v) aminodisiloxanes of the formula(R¹R²N)_(3-x)R_(x)Si—O—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(vi) alkoxydisiloxanes of the formula (RO)_(3-x)R¹_(x)Si—O—Si(OR)_(3-x)R¹ _(x), wherein x is an integer having a value ina range of from 0 to 2, and each R and R¹ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(vii) aminodisilazanes of the formula(R¹R²N)_(3-x)R_(x)Si—NH—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(viii) alkoxydisilazanes of the formula (RO)_(3-x)R¹_(x)Si—NH—Si(OR)_(3-x)R¹ _(x), wherein x is an integer having a value ina range of from 0 to 2, and each R and R¹ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(ix) chloroaminosilanes of the formulae Cl_(4-x)Si(NR¹R²)_(x), wherein xis an integer having a value in a range of from 0 to 3,(R¹R²N)_(3-x)Cl_(x)Si—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of 1 or 2, (R¹R²N)_(3-x)Cl_(x)Si—O—Si(NR¹R²)_(3-x)Cl_(x),wherein x is an integer having a value of 1 or 2, and(R¹R²N)_(3-x)Cl_(x)Si—NH—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of from 1 or 2, and each R¹ and R² is independentlyselected from among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(x) cyclosiloxanes and cyclosilazanes of the formulae:

wherein n is an integer having a value in the range of from 0 to 4, andeach R¹ and R² is selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ dialkylamino, andC₁-C₆ alkoxide;(xi) linear polysiloxanes and polysilazanes;(xii) silicon compounds of general formulae R_(4-x)SiL_(x) wherein x isan integer having a value of from 1 to 3, andL_(3-x)R_(x)Si—SiL_(3-x)R_(x), wherein x is an integer having a value offrom 0 to 2, L is selected from isocyanato (NCO), methylethylketoxime(R¹R²C═N—O—), trifluoroacetate (CF₃OCO), triflate (CF₃SO₃), acyloxy(ROCO), β-diketonate (R¹COCHCOR²), β-diketiminate(R¹CNR²CHCOR³),β-diiminate (R¹CNR²CHCNR²R³), amidinate (RC(NR¹)₂), guanidinate(R¹R²N)C(NR³)₂ alkylamino (NR¹R²), hydride, alkoxide (RO), and formato(HCOO) and each R, R¹, R², and R³ is independently selected from amonghydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, andC₆-C₁₃ aryl;(xiii) oxiranylsilanes of the formulae

wherein x is an integer having a value in a range of from 0 to 3, n isan integer having a value in a range of 0 to 3, and each R¹, R², and R³is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ alkylamino, and C₁-C₆alkoxide;(xiv) silicon precursors containing ethylacetate groups, of the formula(ROCOCH₂CH₂)_(x)Si(OR¹)_(4-x), wherein x is an integer having a value ina range of from 1 to 4, and each of R and R¹ is independently selectedfrom among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(xv) (tBuHN)₂(H₂N)Si—Si(NH₂)(NHtBu)₂ wherein tBu is tertiary butyl; and(xvi) pre-polymer partial hydrolysis products of the foregoing compounds(i)-(xv).

Another aspect of the invention relates to a method of forming an oxidematerial in a trench structure of a substrate for filling thereof, saidmethod comprising depositing oxide precursor material on the substratefor filling of the trench structure, wherein the oxide precursormaterial comprises germanium and silicon.

A further aspect of the invention relates to a microelectronic devicestructure, comprising a substrate having a trench structure formedtherein, wherein the trench structure is filled with a Ge/Si oxidecomposition.

In another aspect, the invention relates to a method of forming an oxidefill material in a trench, comprising depositing the oxide fill materialfrom a precursor composition including a suppressor, to suppress seamformation.

Still another aspect of the invention relates to a method of suppressingadverse seam effects in fill of a trench structure of a substrate with asilicon material oxidizable to form silicon dioxide, said methodcomprising incorporating a germanium precursor in said silicon material.

The invention relates in another aspect to a microelectronic devicestructure, including a trench at least partially filled with a GeO₂/SiO₂mixture.

Another aspect of the invention relates to a method of conducting aTEOS/O₃ process to fill a trench structure in a substrate, comprisingadding a hydroxyl functional compound to said TEOS.

Yet another aspect of the invention relates to a method of filing atrench in a substrate, comprising carrying out a TEOS/ozone process toform silicon oxide material in the trench, with addition to the TEOS ofan aldehyde.

A further aspect of the invention relates to a method of filing a trenchin a substrate, comprising carrying out a TEOS/ozone process to formsilicon oxide material in the trench, wherein TEOS is deposited insubstrate in a composition comprising ethylene glycol and isopropylalcohol.

Other aspects, features and embodiments of the invention will be morefully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of a high aspect ratio trenchstructure in which the trench contains silicon dioxide formed from aprecursor of the present invention that is cured under low temperatureconditions to yield silicon dioxide of a substantially void-freecondition with substantially uniform density throughout its bulk volume,in the trench.

FIGS. 2 and 3 show schematic representations of a microelectronic devicestructure in which deposition of the trench-filling material is beingcarried out with suppressor in the deposited fill material, with FIG. 3showing the effect of suppressor on growth of the oxide material in thetrench.

DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS THEREOF

The present invention relates variously to trench structures, andprecursors and processes useful for forming such trench structures.

As used herein, “low temperature” means temperature below 400° C.

The term “flow fill” in reference to the precursor material of thepresent invention refers to material that in introduction to a highaspect ratio trench is self-leveling within the trench to form a bulkvolume of the material in contact with the trench wall and floorsurfaces.

The term “high aspect ratio” in reference to a trench in amicroelectronic device substrate means a ratio of at least 3:1 ofdepth:width of the trench. In one preferred embodiment, the trench has adepth:width ratio in a range of from 3:1 to 10:1. In another preferredembodiment, the trench has a depth:width ratio of at least 5:1.

As used herein and in the appended claims, the singular forms “a”,“and”, and “the” include plural referents unless the context clearlydictates otherwise.

As used herein, the identification of a carbon number range, e.g., inC₁-C₆ alkyl, or C₁-C₁₂ alkyl, is intended to include each of thecomponent carbon number moieties within such range, so that eachintervening carbon number and any other stated or intervening carbonnumber value in that stated range, is encompassed, it being furtherunderstood that sub-ranges of carbon number within specified carbonnumber ranges may independently be included in smaller carbon numberranges, within the scope of the invention, and that ranges of carbonnumbers specifically excluding a carbon number or numbers are includedin the invention, and sub-ranges excluding either or both of carbonnumber limits of specified ranges are also included in the invention.Accordingly, C₁-C₁₂ alkyl is intended to include methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl,including straight chain as well as branched groups of such types. Ittherefore is to be appreciated that identification of a carbon numberrange, e.g., C₁-C₁₂, as broadly applicable to a substituent moiety,enables, in specific embodiments of the invention, the carbon numberrange to be further restricted, as a sub-group of moieties having acarbon number range within the broader specification of the substituentmoiety. By way of example, the carbon number range e.g., C₁-C₁₂ alkyl,may be more restrictively specified, in particular embodiments of theinvention, to encompass sub-ranges such as C₁-C₄ alkyl, C₂-C₈ alkyl,C₂-C₈ alkyl, C₃-C₅ alkyl, or any other sub-range within the broad carbonnumber range. It therefore is to be understood that any of the carbonnumbers in the specified range may be selected as a respective lowerlimit or upper limit value of the number of carbon atoms in thespecified substituent, so that all possible permutations of sub-rangesare to be regarded as being identically set forth herein.

In like manner, although a specific features, aspects, examples andembodiments are described in particular arrangements of the inventivesubject matter, it is contemplated that such features, aspects, examplesand/or embodiments may be selectively aggregated with one another, inpermutations, combinations and sub-combinations thereof, within thecontemplation and scope of the invention, and are to be regarded asbeing identically set forth herein.

The silicon dioxide precursors suitable for forming silicon dioxidefull-fill high aspect ratio trench structures in the practice of theinvention are flow tillable into high aspect trench structures and curerapidly at low temperature to form silicon dioxide of a substantiallyvoid-free and crack-free condition with substantially uniform densitythroughout bulk volume of the cured silicon dioxide.

Precursors generally useful in the broad practice of the presentinvention include, without limitation, precursor silicon compoundsselected from among the following:

(i) aminosilanes of the formula (R¹R²N)_(4-x)SiR_(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R, R¹, and R²is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(ii) alkoxysilanes of the formula (RO)_(4-x)SiR¹ _(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iii) alkoxydisilanes of the formula (RO)_(3-x)R¹ _(x)Si—Si(OR)_(3-x)R¹_(x), wherein x is an integer having a value in a range of from 0 to 2,and each R and R¹ is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(iv) aminodisilanes of the formula(R¹R²N)_(3-x)R_(x)Si—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched or unbranched C₁-C₆alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(v) aminodisiloxanes of the formula(R¹R²N)_(3-x)R_(x)Si—O—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(vi) alkoxydisiloxanes of the formula (RO)_(3-x)R¹_(x)Si—O—Si(OR)_(3-x)R_(x), wherein x is an integer having a value in arange of from 0 to 2, and each R and R¹ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(vii) aminodisilazanes of the formula(R¹R²N)_(3-x)R_(x)Si—NH—Si(NR¹R²)_(3-x)R_(x), wherein x is an integerhaving a value in a range of from 0 to 2, and each R, R¹, and R² isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(viii) alkoxydisilazanes of the formula (RO)_(3-x)R¹_(x)Si—NH—Si(OR)_(3-x)R_(x), wherein x is an integer having a value in arange of from 0 to 2, and each R and R¹ is independently selected fromamong hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl,and C₆-C₁₃ aryl;(ix) chloroaminosilanes of the formulae Cl_(4-x)Si(NR¹R²)_(x), wherein xis an integer having a value in a range of from 0 to 3,(R¹R²N)_(3-x)Cl_(x)Si—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of 1 or 2, (R¹R²N)_(3-x)Cl_(x)Si—O—Si(NR¹R²)_(3-x)Cl_(x),wherein x is an integer having a value of 1 or 2, and(R¹R²N)_(3-x)Cl_(x)Si—NH—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of from 1 or 2, and each R¹ and R² is independentlyselected from among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(x) cyclosiloxanes and cyclosilazanes of the formulae:

wherein n is an integer having a value in the range of from 0 to 4, andeach R¹ and R² is selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ dialkylamino, andC₁-C₆ alkoxide;(xi) linear polysiloxanes and polysilazanes;(xii) silicon compounds of general formulae R_(4-x)SiL_(x) wherein x isan integer having a value of from 1 to 3, andL_(3-x)R_(x)Si—SiL_(3-x)R_(x) wherein x is an integer having a value offrom 0 to 2, L is selected from isocyanato (NCO), methylethylketoxime(R¹R²C═N—O—), trifluoroacetate (CF₃OCO), triflate (CF₃SO₃), acyloxy(ROCO), β-diketonate (R¹COCHCOR²), β-diketiminate(R¹CNR²CHCOR³),β-diiminate (R¹CNR²CHCNR²R³), amidinate (RC(NR¹)₂), guanidinate(R¹R²N)C(NR³)₂ alkylamino (NR¹R²), hydride, alkoxide (RO), and formato(HCOO) and each R, R¹, R², and R³ is independently selected from amonghydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, andC₆-C₁₃ aryl;(xiii) oxiranylsilanes of the formulae

wherein x is an integer having a value in a range of from 0 to 3, n isan integer having a value in a range of 0 to 3, and each R¹, R², and R³is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ alkylamino, and C₁-C₆alkoxide;(xiv) silicon precursors containing ethylacetate groups, of the formula(ROCOCH₂CH₂)₈Si(OR¹)_(4-x), wherein x is an integer having a value in arange of from 1 to 4, and each of R and R¹ is independently selectedfrom among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl;(xv) (tBuHN)₂(H₂N)Si—Si(NH₂)(NHtBu)₂ wherein tBu is tertiary butyl; and(xvi) pre-polymer partial hydrolysis products of the foregoing compounds(i)-(xv).

The above precursor compounds are readily synthesized within the skillof the art, for use in precursor compositions and applications of thepresent invention.

The precursor compositions of the invention in one specific aspectinclude aminosilanes, which hydrolyze rapidly in exposure to moisture,water and protic solvents. Ammonia, amines and disilanes can be employedto catalyze the condensation reaction, in the curing of the precursorcomposition. Precursors that form silyl radicals or ligands that readilyundergo thermal decomposition (e.g. formate via decarboxylation of CO₂)are also included.

In another specific aspect of the invention, precursor compositions areemployed, which include those of the formulae: (RO)_(4-x)SiH_(x),wherein x is an integer having a value of from 0 to 3,H_(4-x)Si(NR₂)_(x), wherein x is an integer having a value of from 1 to4, H_(4-x)Si(NHR)_(x), wherein x is an integer having a value of from 1to 4, (RO)_(3-x)H_(x)Si—Si(OR)_(3-x)H_(x), wherein x is an integerhaving a value of from 0 to 2, (NR¹R²)_(3-x)H_(x)Si—Si(NR¹R²)_(3-x)H_(x)wherein x is an integer having a value in a range of from 0 to 2, andeach R, R¹, R² is independently selected from among hydrogen, andbranched and unbranched C₁-C₆ alkyl.

In another aspect of the invention, precursor compositions are employed,which comprise silicon precursors in which the silicon atom iscoordinated with ligands including at least one of isocyanato,methylethylketoxime, trifluoroacetate, triflate (F₃SO₃H), alkylamines,hydrides, alkoxides, disilanes, and formato. The resulting Si(OH)₄ solscan be condensed by various techniques, including for example: ammoniaflow into the aqueous solution of the precursor; addition ofco-reactants such as silicon tetrachloride, e.g., 0.05-5% SiCl₄, to analkoxysilane (e.g., tetraethylorthosilicate (TEOS),dibutoxydiacetoxysilane (DBDAS), (EtO)₃SiH, etc.) to generate a smallamount of an acid catalyst species; or addition of a silane (Si—H) ordisilane (Si—Si) precursor such as hexaethylaminodisilane (HEADS).

Another approach to catalyzing condensation in a further aspect of theinvention involves mixing a small amount of a chloroaminosilane, e.g.,0.05-5% Cl_(4-x)Si(NR₂)_(x), wherein x is an integer having a value in arange of from 1 to 3, to the corresponding aminosilaneH_(4-x)Si(NR₂)_(x) wherein x has the same integer value of from 1 to 3.

In a similar manner, mixtures of chloro-substituted silanes andchloro-substituted disilanes can be added to alkoxysilane precursors inan amount, e.g., 0.05-5% by weight, based on the weight of the silicondioxide precursor and the chloro compound, which is sufficient togenerate catalytically effective species for the condensation reaction.

One preferred aminosilane precursor of the invention ishexaethylaminodisilane (HEADS), which rapidly condenses to SiO₂ in thepresence of water or moisture. Other preferred alkylaminosilaneprecursors include (tBuHN)₂(H₂N)Si—Si(NH₂)(NHtBu)₂ and Si(NMe₂)₄.

One preferred group of silicon dioxide precursors of the inventionincludes the precursors (1)-(12) set forth below.

wherein OAc in formula (2) is acetoxy (CH₃C(O)O—), Me in formulae (3)and (4) is methyl, Et in formulae (1), (6), (7) and (11) is ethyl, tBuin formulae (2) and (5) is tertiary butyl, and R in the OR groups offormula (8) is branched or unbranched C₁-C₆ alkyl.

For efficient processing, the gap filling of the trench by flow filltechniques should be complete in a period of less than 10 minutes,preferably not exceeding five minutes, e.g., a period of 3-5 minutes.

The silicon dioxide precursor is deposited into the trench cavity by afull fill technique, such as chemical vapor deposition, atomic layerdeposition, or other vapor-phase contacting of the substrate with theprecursor, conducted at low temperature (<400° C.), preferably below350° C., to cause the silicon dioxide precursor to enter and fill thetrench. The precursor composition full filled in the trench is exposedto water or moisture and hydrolyzes, subsequently undergoing acondensation reaction to form the silicon dioxide product material.

The silicon dioxide material deriving from the precursor of theinvention next is advantageously subjected to post-cure treatment, toeffect densification of the silicon dioxide. The mass of silicon dioxidematerial in the trench constitutes a bulk mass that is in contact withthe wall surfaces and floor surface of the trench, forming a continuousmass in the trench that is homogeneous and substantially void free incharacter.

Any suitable post-cure treatment may be employed for the formed silicondioxide material in the trench to densify the silicon dioxide materialthat has been formed from the precursor by hydrolysis and condensationreactions. Specific post-cure treatment techniques that mayadvantageously be employed in specific embodiments of the inventioninclude, without limitation, exposure of the flow filled material tooxygen, ultraviolet radiation, and/or low-temperature heating.

FIG. 1 is a schematic representation of a high aspect ratio trenchstructure including a silicon dioxide full filled trench, as formed byuse of a precursor of the invention.

As shown in FIG. 1, the high aspect ratio trench structure 10 includes amicroelectronic device substrate 12 with a top surface 14 and a bottomsurface 16. The substrate includes a trench 18 bounded by side wallsurfaces 20 and floor surface 22. The trench cavity in this structure isfilled with a mass of silicon dioxide 24 that is in contact with thewall and floor surfaces 18, 20, 22, and is substantially void-free andof substantially uniform density throughout its bulk volume.

In preferred practice, the substantially void-free character of thesilicon dioxide formed in the trench is readily confirmed byporosimetry, permeability criteria, SEM cross-sectioning, or otherconventional techniques for morphological characterization to determinepresence of voids.

The foregoing precursors and methodology of the invention enableeffective formation of full fill trench structures with silicon dioxidethat is curable under low temperature conditions to yield silicondioxide of a substantially void-free condition with substantiallyuniform density throughout its bulk volume.

Another aspect of the invention relates to a Ge/Si oxide composition forgap filling in applications such as fill of memory device trenches. GeO₂has a much lower viscosity than SiO₂. The invention in this aspectcontemplates the use of a Si_(x)Ge_(1-x)O₂ to enable sufficient atomicrearrangement to occur for healing of the seam produced by coalescenceof side-wall growth in the trench, thereby removing any non-uniformstrain within the gap fill. This in turn enables a uniform removal rateto be achieved, with respect to cleaning chemistry exposure insubsequent processing of the device structure.

In the use of Si_(x)Ge_(1-x)O₂ for gap filling, the ratio of germaniumto silicon in the film is advantageously in a range of from 0.005 to0.25 (with x having a value in the formula Si_(x)Ge_(1-x)O₂ of 0.75 to0.995), in order to appropriately minimize germanium content forachievement of acceptable dielectric properties.

In the use of such Ge/Si oxide compositions, only sufficient flow tofill the seam and remove strain non-uniformity is required, and hightemperatures can be tolerated in the curing operation. Thesecharacteristics enable the amount of added germanium to be minimized, sothat other film properties can be optimized. A preferred germaniumprecursor for such purpose is selected from among germanium alkoxides:R_(4-x)Ge(OR¹)_(x), R_(4-x)Ge(NR¹R²)_(x), and R_(4-x)GeH_(x); whereinx=0−4 and each R, R¹, R² is independently selected from among branchedand unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl.

A preferred embodiment uses the tetra-alkoxygermanes, Ge(OMe)₄ (TMOG) orGe(OEt)₄ (TEOG).

Using germanium alkoxides in a tetraethylorthosilicate (TEOS)/ozone (O₃)process has the advantage that film smoothness can be substantiallyimproved. This factor is particularly important for gap fill, since theseam width is likely to be dependent on the roughness of the growthsurfaces when coalescence occurs, as the sidewall growth elements meetone another.

The invention in another aspect relates to use of suppressors for bottomup gap fill. This aspect of the invention takes advantage of the factthat a deposition process characterized by a higher growth rate at thebottom of the trench than at the upper regions thereof will result in areduced seam length, even offering the potential for elimination of theseam. The invention therefore contemplates suppression of depositionoutside of the trench relative to the bottom of the trench, using a“suppressor” chemical species. The concentration of such suppressor canbe reduced within the trench due to slower transport into the trenchfeatures relative to transport to the wafer surface. In order togenerate low concentrations within the trench, some consumption ofsuppressor species is required, e.g. by decomposition or reaction in thegas phase or on the surface, such as may be effected by ozone-mediatedoxidation.

In the tetraethylorthosilicate (TEOS)/ozone process, addition ofmethanol can be employed to planarize deposition profiles. Lowerdeposition rates can occur in very high aspect ratio structures due toaccumulation of TEOS/O₃ reaction products, which in turn act to suppressgrowth. The TEOS/O₃ reaction products can include acetaldehyde and/orpossible oxirane, and active species may include hydrocarbons withcarbonyl functionality, as a product of oxidation of alcohols withozone.

More generally, a wide variety of hydrocarbon species can be employed assuppressors to modify the deposited film profile within a trench. Theseinclude hydrocarbons with one or more carbonyl groups and/or one or morehydroxy groups.

As used herein, a “suppressor” is a species that reduces growth ratewhen introduced with precursor on a substrate.

FIG. 2 is a schematic representation of a microelectronic devicestructure 50 including a substrate 52 in which a trench 58, bounded bysidewalls 54 and floor 56, has been formed.

FIG. 2 shows suppressor being in the deposited material 56 including theprecursor, and in FIG. 3, the formation of oxide 60 is shown on the mainsurface of the device structure 50 and in the trench 58. The lowertransport rate of suppressor into the trench combined with suppressorconsumption produces reduced suppressor concentrations at the bottom ofthe trench, with correspondingly increased oxide growth. This effect isstronger as the trench closes.

The ideal suppressor has a low gas diffusion rate and high molecularweight, and functions to strongly suppress film growth. The suppressoris consumed to effect depletion thereof, to an extent dependent on thedegree of mass transport in the deposition system. Ideally, thesuppressor is oxidized by ozone, and undergoes decomposition andreaction with tetraethylorthosilicate. Control of the oxide growth ratein the TEOS/O₃ process can be effected by surface reaction control.Preferred suppressor chemistries in specific applications includealcohol and alcohol oxidation products.

In using GeO₂/SiO₂ mixtures for gap fill of trenches, advantage is takenof the substantially lower viscosity of GeO₂/SiO₂, particularly underannealing conditions. In GeO₂/SiO₂ mixtures with minimal GeO₂/SiO₂content, substantial strain relief is achievable as a result of thesubstantially lower viscosity of GeO₂/SiO₂, and at moderate GeO₂/SiO₂content, sufficient flow character is present for healing of narrow seamstructures in trench fill material. Germanium alkoxides can be used toachieve good GeO₂/SiO₂ mixtures for trench fill. The advantages ofgermanium in such GeO₂/SiO₂ mixtures, include, in relation to SiO₂alone, higher flow at elevated temperatures, reduced moisture content,reduced film roughness and highly uniform chemical reactivity. Thepresence of germanium is appropriately limited to avoid undue etch ratesin exposure to etchants such as hydrogen fluoride, and avoidance ofleakage and breakdown strength issues in the cured fill material.Further, it may be desirable to limit or even avoid hydrogenenvironments in annealing operations, in order to avoid reduction ofGeO₂/SiO₂ to GeO.

Reactions involved in sol-gel solution chemistry for formation of oxidefill material are set out below, including the reaction involved in thehydrolysis of TEOS:

and (poly) condensation of silanols:

In this reaction scheme, for every silanol bridge formed, one watermolecule is consumed. The gel structure is dependent on reactantconcentrations of TEOS and water, as well as pH of the deposited fillmaterial. In acidic solutions, hydrolysis reaction tends to go tocompletion and less cross-linked chains are formed, withreesterification (reverse hydrolysis) being occasionally observed. Inbasic solution, more highly cross-linked structures are formed, withhigher water concentrations promoting hydrolysis and impedingcondensation, resulting in higher cross-linked density in the oxidematerial.

Concerning acid and base catalyzed hydrolysis, acid catalyzed hydrolysisproceeds by the following electrophilic mechanism involving H₃O⁺:

and base catalyzed hydrolysis proceeds by a nucleophilic reactionmechanism according to the following reaction:

The lower electron density on the silicon atoms as a result of silanolformation, in relation to alkoxy groups, produces a preferred attack ofsilicon centers with more silanol groups, in base catalyzed systems, anda preferred attack of silicon centers with more alkoxy groups, in acidcatalyzed systems. Accordingly, there is a preference for chainextension in acidic solutions, and a preference for cross-linking inbasic solutions.

In the TEOS/ozone system for deposition of oxide film material, theTEOS/ozone reaction products or oxidation products of the alkoxy ligandare set out in Table 1 below:

TABLE 1 Species Name CH₃COOH acetic acid CH₃CHO acetaldehyde HCOOHformic acid CH₂O formaldehyde CO carbon monoxide CO₂ carbon dioxide H₂Owater ≡SiOH Silanol

In the TEOS/ozone process, alcohol addition yields enhanced flowcharacteristics, particularly when methanol is utilized. In the alcoholoxidation reaction, one equivalent of water and one equivalent ofcarboxylic acid are formed after double oxidation of the primaryalcohol:

Alcohol addition in the TEOS/ozone process can utilize any suitablealcohol species, with the efficacy of specific alcohols being readilyempirically determinable within the skill in the art, based on thedisclosure herein. Alcohols such as methanol, formic acid, acetic acidand propionic acid may be used in specific embodiments of the invention.More generally, hydroxy-functional compounds may be used in the TEOS/O₃process to enhance the character of the trench fill operation.

In specific implementations, hydroxy-functional species can includediols, e.g., ethylene glycol, and halogenated alcohols such as2,2,2-tricholoroethanol.

Dicarboxylic acids can be formed from diols, by reactions such as thefollowing:

Such use of polyol species produces stronger acid than the acid productformed from primary alcohols. Even stronger carboxylic acids can beformed from oxidation of halogenated alcohols, e.g., as shown by thefollowing reaction. The pK_(a) of trichloracetic acid is 0.77.

Thus, the invention achieves improved gap filling of trench structuresby use of germanium and silicon oxide mixtures, as well as by use ofalcoholic or other suppressor species to avoid or minimize seamformation issues in the fill process.

The invention therefore overcomes the problems associated with theTEOS/ozone process in respect of seam formation in trench structures,particularly those with high aspect ratios.

More generally, the chemistry of silicon dioxide synthesis from alkoxidesilicon precursors in aqueous solutions is fairly well understood. Inthe sol-gel process, the hydrolysis of TEOS can be either base or acidcatalyzed to form a silanol group and two equivalents of ethanol. In asubsequent reaction step, two silanols condense to form a siloxanebridge and liberate one equivalent of water. After condensation, thereare generally some remaining silanols and possibly unreacted alkoxygroups and reaction products. The result is a semi-solid mixture that isreferred to as a gel. If SiO₂ is desired, the gel then is heated toremove byproducts and allow further condensation (calcination). Thefinal structure, with respect to bond angles and defects, is determinedby the solution pH, water and TEOS concentrations and calcinationconditions.

The hydrolysis and condensation of TEOS and solutions proceeds by anelectrophilic reaction mechanism in acid catalyzed solutions, as opposedto nucleophilic reaction in base catalyzed solutions. One consequence ofthis is that alkoxy groups on less hydrolyzed silicons are less stablewith respect to condensation than those on more hydrolyzed siliconcenters. This favors formation of chain structures. Conversely, basecatalyzed condensation more readily occurs with silicon centers thathave been hydrolyzed. This results in formation of more fully hydrolyzedspecies before condensation and therefore more cross-linking.

Water is consumed during hydrolysis and liberated during condensation.Accordingly, higher water concentrations promote hydrolysis and impedecondensation. The result is higher cross-link density.

In the TEOS/ozone process, film formation also occurs by silanolformation followed by condensation of silanol groups to form siloxanebridges. Oxidation of alkoxy groups is also present (producingacetaldehyde, formaldehyde, CO, CO₂, and silanol groups). The presenceof water and acid in TEOS/ozone processes affords the possibility ofemploying hydrolysis reactions to form SiO₂ films.

Oxidation of alcohol added to the TEOS/ozone process results in thepresence of carboxylic acids. The acids formed from smaller primaryalcohols have lower pK_(a) and may be more effective in catalyzinghydrolysis.

Accordingly, species that oxidize in the presence of ozone can be usedto control the chemical reactions during a TEOS/ozone process. Forexample, double oxidation of alcohols produces both water and acarboxylic acid (acetic acid in the case of ethanol). Addition of theintermediate (acetaldehyde) can produce acid without forming water, andtherefore can be employed to control the acid/H₂O ratio.

This has some advantages over direct addition of water and acid. Stablemixtures of alkoxide and alcohol/aldehydes or other organic species canbe formed, whereas mixtures of acids and/or water and alkoxides willreact over time. Liquid mixtures can allow for more accurate control ofthe ratio of reactant, and also allow in-situ generation of species thatmay not be stable enough for efficient delivery. Use of an aldehyde doesnot add water, and it therefore requires water from the condensationreaction to enable further hydrolysis to take place. Another potentialadvantage is flexibility in avoiding less safe and less stablealkoxides. For example, TEOS is preferred over tetramethoxysilane(TMOS), because TMOS is more toxic and more reactive to atmosphericcontamination. TMOS, however, has better flowability. If an importantdifference is the presence of formic acid as the product of TMOSdecomposition, then a similar result could be achieved with TEOS andmethanol.

Stronger acids can more readily catalyze hydrolysis. These strongeracids can be formed from ethylene glycol or from halogenated alcoholsuch as trichloroethanol or trifluoroethanol. Oxidation of ethyleneglycol results in oxalic acid (pK_(a)=1.23), and oxidation oftrichloroethanol and trifluoroethanol results in trichloroacetic acidand trifluoroacetic acid, respectively (pK_(a)=0.77 and 0.30,respectively).

For single solution approaches, the additive employed in the TEOS/ozoneprocess must be soluble in the alkoxide. In some cases, a co-solvent maybe required to form a solution. For example, TEOS and ethylene glycolhave very limited mutual solubility, but the addition of isopropylalcohol allows the solution to be formed.

It will therefore be seen that the efficacy of the TEOS/ozone processcan be substantially increased by addition of additives as disclosedherein.

The features and advantages of the invention are more fully shown by thefollowing non-limiting examples of gap fill processes.

Gap Fill Process Examples

Deposition was carried out in an Applied Materials P5000 reactor withthe TEOS/ozone process. Void fraction was found by measuring the voidarea in SEM cross-sections after cleaving and staining in 200:1 H₂O:HF.Stain times were chosen to result in 5 nm removal of SiO2 from blanketfilm witness pieces deposited in the same run. Results are set out belowin the tables for Examples 1, 2 and 3.

Example 1

Parameter Value TEOS first Stabilize in TEOS 90 seconds beforedeposition Pressure 500Torr Susceptor Temperature 425 C Formulation:IPA/Methanol/TEOS 4:4:1 Liquid Flow 0.433 cc/min Ozonator feed gas 10SLMO2 + 100 ppm N2 Ozone Concentration 12% Susceptor spacing 420 mils Void% Annealed (800 C 30 min) 10.57 Void % As deposited 6.88 Rate 4.5 A/sectime for 2000A 444 seconds

Example 2

Parameter Value TEOS first Stabilize in TEOS 90 seconds beforedeposition Pressure 500Torr Susceptor Temperature 425 C Formulation:IPA:Ethanol:TMOG:TEOS 0.05:0.10:0.05:1 Liquid Flow 0.35 cc/min Ozonatorfeed gas 10SLM O2 + 100 ppm N2 Ozone Concentration 15% Susceptor spacing420 mils Ge content (film) 2 atomic % Void % Annealed (800 C 30 min)3.59% Void % As deposited 1.86 Rate 10 A/sec

Example 3

Parameter Value TEOS first Stabilize in TEOS 90 seconds beforedeposition Pressure 500Torr Susceptor Temperature 425 C Formulation:IPA:Ethanol:TMOG:TEOS 0.05:0.10:0.20:1 Liquid Flow 0.35 cc/min. Ozonatorfeed gas 10SLM O2 + 100 ppm N2 Ozone Conc 15% Susceptor spacing 420 milsVoid % Annealed (800 C 30 min) 1.34% Void % As deposited 0.71 Rate 6A/sec

While the invention has been has been described herein in reference tospecific aspects, features and illustrative embodiments of theinvention, it will be appreciated that the utility of the invention isnot thus limited, but rather extends to and encompasses numerous othervariations, modifications and alternative embodiments, as will suggestthemselves to those of ordinary skill in the field of the presentinvention, based on the disclosure herein. Correspondingly, theinvention as hereinafter claimed is intended to be broadly construed andinterpreted, as including all such variations, modifications andalternative embodiments, within its spirit and scope.

1-124. (canceled)
 125. A precursor composition, comprising: a germaniumprecursor; a silicon precursor; alcohol; and an oxidant.
 126. Thecomposition of claim 125, wherein the composition is in a vapor phase.127. the composition of claim 125, wherein the germanium precursorcomprises TMOG.
 128. the composition of claim 125, wherein the siliconprecursor comprises tetraethylorthosilicate.
 129. The composition ofclaim 125, wherein the alcohol is selected from the group consisting ofisopropyl alcohol, ethanol, and mixtures thereof.
 130. The compositionof claim 125, wherein the oxidant comprises ozone.
 131. A method ofprocessing a substrate including a trench or gap structure therein,comprising contacting the substrate with a composition according toclaim 125, under conditions effecting deposition of a germanium- andsilicon-containing oxide in the trench or gap structure.
 132. A fullfill trench structure comprising a microelectronic device substratehaving a high aspect ratio trench therein and a full filled mass ofsilicon dioxide in said trench, said silicon dioxide being of asubstantially void-free character and having a substantially uniformdensity throughout its bulk mass, as formed by full fill of the trenchwith a silicon dioxide precursor composition, and hydrolysis andcondensation chemical reactions of the precursor composition to form thesilicon dioxide full filled mass in the trench.
 133. The full filltrench structure of claim 132, wherein said precursor compositioncomprises a precursor silicon compound selected from the groupconsisting of: (i) aminosilanes of the formula (R¹R²N)_(4-x)SiR_(x),wherein x is an integer having a value in a range of from 0 to 3, andeach R, R¹, and R² is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(ii) alkoxysilanes of the formula (RO)_(4-x)SiR¹ _(x), wherein x is aninteger having a value in a range of from 0 to 3, and each R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (iii) alkoxydisilanes ofthe formula (RO)_(3-x)R¹ _(x)Si—Si(OR)_(3-x)R¹ _(x), wherein x is aninteger having a value in a range of from 0 to 2, and each R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (iv) aminodisilanes ofthe formula (R¹R²N)_(3-x)R_(x)Si—Si(NR¹R²)_(3-x)R_(x), wherein x is aninteger having a value in a range of from 0 to 2, and each R, R¹, and R²is independently selected from among hydrogen, branched or unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (v) aminodisiloxanes ofthe formula (R¹R²N)_(3-x)R_(x)Si—O—Si(NR¹R²)_(3-x)R_(x), wherein x is aninteger having a value in a range of from 0 to 2, and each R, R¹, and R²is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (vi) alkoxydisiloxanesof the formula (RO)_(3-x)R¹ _(x)Si—O—Si(OR)_(3-x)R¹ _(x), wherein x isan integer having a value in a range of from 0 to 2, and each R and R¹is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (vii) aminodisilazanesof the formula (R¹R²N)_(3-x)R_(x)Si—NH—Si(NR¹R²)_(3-x)R_(x), wherein xis an integer having a value in a range of from 0 to 2, and each R, R¹,and R² is independently selected from among hydrogen, branched andunbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (viii)alkoxydisilazanes of the formula (RO)_(3-x)R¹ _(x)Si—NH—Si(OR)_(3-x)R¹_(x), wherein x is an integer having a value in a range of from 0 to 2,and each R and R¹ is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(ix) chloroaminosilanes of the formulae Cl_(4-x)Si(NR¹R²)_(x), wherein xis an integer having a value in a range of from 0 to 3,(R¹R²N)_(3-x)Cl_(x)Si—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of 1 or 2, (R¹R²N)_(3-x)Cl_(x)Si—O—Si(NR¹R²)_(3-x)Cl_(x),wherein x is an integer having a value of 1 or 2, and(R¹R²N)_(3-x)Cl_(x)Si—NH—Si(NR¹R²)_(3-x)Cl_(x), wherein x is an integerhaving a value of from 1 or 2, and each R¹ and R² is independentlyselected from among hydrogen, branched and unbranched C₁-C₆ alkyl, C₃-C₈cycloalkyl, and C₆-C₁₃ aryl; (x) cyclosiloxanes and cyclosilazanes ofthe formulae:

wherein n is an integer having a value in the range of from 0 to 4, andeach R¹ and R² is selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ dialkylamino, andC₁-C₆ alkoxide; (xi) linear polysiloxanes and polysilazanes; (xii)silicon compounds of general formulae R_(4-x)SiL_(x) wherein x is aninteger having a value of from 1 to 3, and L_(3-x)R_(x)Si—SiL_(3-x)R_(x)wherein x is an integer having a value of from 0 to 2, L is selectedfrom isocyanato (NCO), methylethylketoxime (R¹R²C═N—O—),trifluoroacetate (CF₃OCO), triflate (CF₃SO₃), acyloxy (ROCO),β-diketonate (R¹COCHCOR²), β-diketiminate(R¹CNR²CHCOR³), β-diiminate(R¹CNR²CHCNR²R³), amidinate (RC(NR¹)₂), guanidinate {(R¹R²N)C(NR³)₂},alkylamino (NR¹R²), hydride, alkoxide (RO), and formato (HCOO) and eachR, R¹, R², and R³ is independently selected from among hydrogen,branched and unbranched C₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl;(xiii) oxiranylsilanes of the formulae

wherein x is an integer having a value in a range of from 0 to 3, n isan integer having a value in a range of 0 to 3, and each R¹, R², and R³is independently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, C₆-C₁₃ aryl, C₁-C₆ alkylamino, and C₁-C₆alkoxide; (xiv) silicon precursors containing ethylacetate groups, ofthe formula (ROCOCH₂CH₂)_(x)Si(OR¹)_(4-x), wherein x is an integerhaving a value in a range of from 1 to 4, and each of R and R¹ isindependently selected from among hydrogen, branched and unbranchedC₁-C₆ alkyl, C₃-C₈ cycloalkyl, and C₆-C₁₃ aryl; (xv)(tBuHN)₂(H₂N)Si—Si(NH₂)(NHtBu)₂ wherein tBu is tertiary butyl; and (xvi)pre-polymer partial hydrolysis products of the foregoing compounds(i)-(xv).
 134. The full fill trench structure of claim 132, wherein saidsilicon dioxide has been further processed for densification thereofafter the hydrolysis and condensation chemical reactions.
 135. The fullfill trench structure of claim 134, wherein said densification iseffected by exposure of the silicon dioxide to at least one of oxygenexposure, ultraviolet radiation, and low-temperature heating.
 136. Amethod of forming an oxide material in a trench structure of a substratefor filling thereof, said method comprising at least one of the stepsof: (i) depositing oxide precursor material on the substrate for fillingof the trench structure, wherein the oxide precursor material comprisesgermanium and silicon; and (ii) depositing the oxide material from aprecursor composition including a suppressor, to suppress seamformation.
 137. The method of claim 136, wherein deposited oxideprecursor material is cured under an ozone atmosphere.
 138. The methodof claim 136, wherein the oxide material precursor comprises a germaniumalkoxide.
 139. The method of claim 136, wherein said oxide precursormaterial is cured to form a GeSi oxide composition in said trenchstructure.
 140. The method of claim 136, comprising depositing the oxidefill material from a precursor composition including a suppressor, tosuppress seam formation.
 141. The method of claim 140, wherein thesuppressor comprises hydroxyl functionality.
 142. The method of claim140, wherein the suppressor comprises at least one hydroxyl functionalsuppressor, selected from the group consisting of alcohols, polyols andglycols.
 143. The method of claim 140, wherein the suppressor comprisesalcohol.
 144. A microelectronic device structure, including a trench atleast partially filled with a GeO₂/SiO₂ mixture.